Easy synthesis of hollow core, bimodal mesoporous shell carbon nanospheres and their application in supercapacitor.

Hollow core, mesoporous shell carbon nanospheres (HCMSs) with large bimodal mesopores (6.4 and 3.1 nm) and high surface area (1704 m(2) g(-1)) have been synthesized by a triconstituent surface co-assembly of monodisperse silica nanospheres method. The resulted HCMS show a high specific capacity of 251 F g(-1) at 50 mV s(-1) in 2 M H(2)SO(4) and long cyclic life.

Determination of acetanilide herbicides in cereal crops using accelerated solvent extraction, solid-phase extraction and gas chromatography-electron capture detector.

A method was developed to determine eight acetanilide herbicides from cereal crops based on accelerated solvent extraction (ASE) and solid-phase extraction (SPE) followed by gas chromatography-electron capture detector (GC-ECD) analysis. During the ASE process, the effect of four parameters (temperature, static time, static cycles and solvent) on the extraction efficiency was considered and compared with shake-flask extraction method. After extraction with ASE, four SPE tubes (graphitic carbon black/primary secondary amine (GCB/PSA), GCB, Florisil and alumina-N) were assayed for comparison to obtain the best clean-up efficiency. The results show that GCB/PSA cartridge gave the best recoveries and cleanest chromatograms. The analytical process was validated by the analysis of spiked blank samples. Performance characteristics such as linearity, limit of detection (LOD), limit of quantitation (LOQ), precision and recovery were studied. At 0.05 mg/kg spiked level, recoveries and precision values for rice, wheat and maize were 82.3-115.8 and 1.1-13.6%, respectively. For all the herbicides, LOD and LOQ ranged from 0.8 to 1.7 µg/kg and from 2.4 to 5.3 µg/kg, respectively. The proposed analytical methodology was applied for the analysis of the targets in samples; only three herbicides, propyzamid, metolachlor and diflufenican, were detected in two samples.

Selective solid-phase extraction using molecularly imprinted polymer for analysis of methamidophos in water and soil samples.

An analytical methodology for the analysis of methamidophos in water and soil samples incorporating a molecularly imprinted solid-phase extraction process using methamidophos-imprinted polymer was developed. Binding study demonstrated that the polymer exhibited excellent affinity and high selectivity to the methamidophos. Evidence was also found by FT-IR analysis that hydrogen bonding between the CO(2)H in the polymer cavities and the NH(2) and P=O of the template was the origin of methamidophos recognition. The use of molecularly imprinted solid-phase extraction improved the accuracy and precision of the GC method and lowered the limit of detection. The recovery of methamidophos extracted from a 10.0 g soil sample at the 100 ng/g spike level was 95.4%. The limit of detection was 3.8 ng/g. The recovery of methamidophos extracted from 100 mL tap and river water at 1 ng/mL spike level was 96.1% and 95.8%, and the limits of detection were 10 and 13 ng/L respectively. These molecularly imprinted solid-phase extraction procedures enabled selective extraction of polar methamidophos successfully from water and soil samples, demonstrating the potential of molecularly imprinted solid-phase extraction for rapid, selective, and cost-effective sample pretreatment.

Metal ion binding to anticoagulation factor II from the venom of Agkistrodon acutus: stabilization of the structure and regulation of the binding affinity to activated coagulation factor X.

Anticoagulation factor II (ACF II) isolated from the venom of Agkistrodon acutus is an activated coagulation factor X (FXa)-binding protein with both anticoagulant and hypotensive activities. The thermodynamics of the binding of alkaline earth metal ions to ACF II and their effects on the stability of ACF II and the binding of ACF II to FXa were investigated by isothermal titration calorimetry, fluorescence, differential scanning calorimetry, and surface plasmon resonance. The binding of ACF II to FXa does not have an absolute requirement for Ca(2+). Mg(2+), Sr(2+), and Ba(2+) can induce the binding of ACF II to FXa. The radii of the cations bound in ACF II crucially affect the binding affinity of ACF II for cations and the structural stability of ACF II against guanidine hydrochloride and thermal denaturation, whereas the radii of cations bound in FXa markedly affect the binding affinity between ACF II and FXa. The binding affinities of ACF II for cations and the capacities of metal-induced stabilization of ACF II follow the same trend: Ca(2+) > Sr(2+) > Ba(2+). The metal-induced binding affinities of ACF II for FXa follow the trend Mg(2+) > Ca(2+) > Sr(2+) > Ba(2+). Although Mg(2+) shows significantly low binding affinity with ACF II, Mg(2+) is the most effective to induce the binding of ACF II with FXa. Our observations suggest that in blood the bindings of Ca(2+) in two sites of ACF II increase the structural stability of ACF II, but these bindings are not essential for the binding of ACF II with FXa, and that the binding of Mg(2+) and Ca(2+) to FXa may be essential for the recognition between FXa and ACF II. Like Ca(2+), the abundant Mg(2+) in blood also plays an important role in the anticoagulation of ACF II.

[Spectroscopy study of binding mechanisms and molecular recognition of methamidophos-specific moleculary imprinted polymer].

A new methamidophos-specific molecularly imprinted polymer (MIP) was synthesized based on non-covalent interaction. The complexes formed between MAP and MAA were evaluated by 1H NMR, FTIR and UV spectrometry. The MAP-MAA complexes of 1 : 2 mole ratio were obtained by cooperative hydrogen bonding and the complexes possessed better stabilization (K = 2.894 x 10(6) L2 x mol(-2). The Infrared spectrometry differences of the MIPs before and after saturated with MAP further indicated that there were carboxyl functional groups in the MIP, which could interact with the template by cooperative hydrogen bonding specifically.

[Determination of cadmium in tobacco using thermospray-chemical vapor generation-AAS system].

A new and sensitive method for the determination of cadmium was developed using thermospray chemical vapor generation AAS system. The sample and KBH4 solutions were introduced into two separate thermospray tubes by peristaltic pumps and then thermosprayed into a reaction tube. The aerosol of the sample and KBH4 were mixed and reacted in the reaction tube, and after gas-liquid separation in a cyclonic spray chamber, the water vapor was removed by a desolvating unit, while the analyte was transferred into the quartz T-cell and determined by AAS. This design improved the stability and sensitivity by thermospray chemical vapor sample introducing technique. The effect of several experimental parameters of the proposed system was optimized. Under the optimized experimental conditions, the detection limits of 18 ng x L(-1) with RSD of 2.1% was obtained for cadmium determination. This method has been successfully applied to the determination of cadmium in tobacco with the recoveries of 94%-103%.

Enantiomeric analysis of anatabine, nornicotine and anabasine in commercial tobacco by multi-dimensional gas chromatography and mass spectrometry.

A fully automated multi-dimensional gas chromatography (MDGC) system with a megabore precolumn and cyclodextrin-based analytical column was developed to analyze the enantiomeric compositions of anatabine, nornicotine and anabasine in commercial tobacco. The enantiomer abundances of anatabine and nornicotine varied among different tobacco. S-(-)-anatabine, as a proportion of total anatabine, was 86.6% for flue-cured, 86.0% for burley and 77.5% for oriental tobacco. S-(-)-nornicotine, as a proportion of total nornicotine, was 90.8% in oriental tobacco and higher than in burley (69.4%) and flue-cured (58.7%) tobacco. S-(-)-anabasine, as a proportion of total anabasine, was relatively constant for flue-cured (60.1%), burley (65.1%) and oriental (61.7%) tobacco. A simple solvent extraction with dichloromethane followed by derivatisation with trifluoroacetic anhydride gave relative standard deviations of less than 1.5% for the determination of the S-(-)-isomers of all three alkaloids. The study also indicated that, a higher proportion of S-(-)-nornicotine is related to the more active nicotine demethylation in the leaf.

[Study of thermal diffusivity by piezoelectric photoacoustic phase].

Piezoelectric photoacoustic phase information can be applied to determine the thermal diffusivity of sample. In actual experiments, the results of phase versus modulation frequency deviate from the theory heavily because of the disturbance of instrumental contribution from the whole detecting system. Considering that the instrumental contribution of phase from PA cell can be ignored reasonably, there will be no additional phase contribution after the piezoelectric PA cell has been replaced by microphone PA cell while the other experimental conditions have been kept invariable. Based on this hypothesis, the conventional photoacoustic cell with microphone is employed to determine the instrumental contribution of whole detecting system by studying the PA phase of solid rare earth complexes. The instrumental contribution of phase was considered to be constant for that the same detecting system was used in both the microphone PA method and piezoelectric PA method. This method has been proved by detecting the thermal diffusivity of aluminium sample. The corrected results of experiments match the theory well, showing that the method of subtracting the instrumental contribution from the original experimental phase can be applied reasonably in relevant chopping frequency region. While in lower chopping frequency region, there will be a little deviation from the theoretical results. The method has been also employed to the photoacoustic detection of leaf, and the thermal diffusivity of leaf can be acquired by studying the piezoelectric photoacoustic phase.

[Spectroscopy and XPS studies on molecular recognition of a molecularly imprinted cotinine-specific polymer].

In the present study, molecular imprinting technique was used to develop a method based on noncovalent interaction for the systhesis of a cotinine-specific polymer. The molecular recognition characteristics of the template polymer were evaluated by UV, IR, XPS and 1H NMR. The results indicated that the interactions should be cooperative hydrogen bonds produced by self-assembling of the template and the monomer. The stoichiometric mole ratio of COT-MAA complex is 1 : 2. Furthermore, nitrogen atom of the pyridine ring and oxygen atom of the lactam group in cotinine molecular are hydrogen-bond acceptors, being the predominant binding sites interacting with the functional monomer.

Determination of pesticide residues in soil by modified matrix solid-phase dispersion and gas chromatography.

Modified matrix solid-phase dispersion (MMSPD) and gas chromatography have been developed for quantitative analysis of various classes of pesticides (pirimicarb, metalaxyl, metolachlor, isopropalin and pendimethalin) in soil. MMSPD used Florisil as dispersant and acetone as solvent. Determination was carried out by gas chromatography with nitrogen-phosphorus detection (GC-NPD). The effect of the residence time of pesticides in soil on the recoveries was studied. MMSPD was compared with continuous liquid-solid extraction (LSE). MMSPD had good extraction efficiency and cleanup efficiency and the extract obtained could be directly subjected to GC analysis without further purification. The method gave recoveries ranging from 93% to 100% with relative standard deviations (RSDs) lower than 10%. The limits of detection (LODs) ranged from 0.2 to 2.0 ng g(-1).

Dynamic ultrasound-assisted extraction of catechins and caffeine in some tea samples.

A novel dynamic ultrasound-assisted extraction (DUAE) device has been constructed for extraction of five catechins and caffeine in solid sample. The accurate, simple, reproducible and sensitive method for the determination of five catechins and caffeine has been developed and validated. A comparison has been made of the efficiencies by employing DUAE and conventionally static ultrasound-assisted extraction (UAE). The proposed method can not only improve extraction efficiency but also decrease time and solvent consumption. The commercial Chinese tea samples, involving green and black teas, are rapidly analyzed by the proposed DUAE method. The linearity, range, selectivity, precision, accuracy, and robustness also showed acceptable values.

Photoacoustic and luminescence spectra study on the effects of chlorine substituent on the energy transfer of Eu(III)-chlorobenzoic acid.

The photoacoustic (PA) amplitude spectra of three complexes of Eu(III) combined with chlorobenzoic acid (Eu(o-ClC6H4CO2)3.H2O, Eu(m-ClC6H4CO2)3.H2O and Eu(p-ClC6H4CO2)3.H2O) have been measured, and the PA phase of the different complexes have been calculated. Both the PA amplitude spectra and the luminescence spectra reflect the variation of the luminescent properties, and the PA phase is directly relative to the relaxation time. Since the relaxation is the process of the intramolecular energy transfer between the ligands and the central ion, the molecular structure of ligand is the important factor to decide the energy gap between the lowest triplet state of ligand and the resonance level of central ion. The effects of chlorine substituent on the molecular structure and energy gap of the complexes have been studied by PA phase and luminescence spectra.

On-line sample digestion using an electromagnetic heating column for the determination of zinc and manganese in tea leaf by flame atomic absorption spectrometry.

A new on-line sample digestion system using electromagnetic induction heating technique was developed for the determination of zinc and manganese in tea leaf by flame atomic absorption spectrometry (FAAS). The homemade electromagnetic heating column (EMHC), whose effective diameter was about 1mm, was composed of a polytetrafluoroethylene (PTFE) outer tube and seven compactly packed PTFE coil-coated iron wires. The pre-digested sample solution was pumped through EMHC and then transferred directly to FAAS for determination. An analytical throughput of 72samplesh(-1) was obtained in the present system. Under optimal condition, the detection limits (3sigma) of zinc and manganese were 4.2mugL(-1) and 3.0mugL(-1), along with relative standard deviations (R.S.D.) of 3.2% and 3.6% respectively for zinc and manganese. Certified reference materials GBW 07602, GBW 07605 and GBW 08505 were analyzed to validate the proposed method, good agreement was achieved between the certified values and the obtained results.

Films coated with molecular imprinted polymers for the selective stir bar sorption extraction of monocrotophos.

The flexibility and simplicity of stir bar sorption extraction (SBSE) have been combined with the selectivity of molecularly imprinted polymers (MIP). Stir bars were coated reproducible with a 180 microm film formed from a formic acid solution of nylon-6 polymer either nonimprinted or imprinted with monocrotophos. Time sorption profiles were measured for the extraction of monocrotophos from dichloromethane at the concentration of 10-200 micromol/L levels with both types of films in order to compare extraction characteristics. The results indicated that the MIP coated layer showed remarkable high affinity toward monocrotophos and equilibrium adsorption was attained rapidly (60 min) in contrast to free standing molecularly imprinted polymer in which equilibrium adsorption was normally attained after several hours. The stir bars coated with MIP films were capable of extracting four structural analogues of monocrotophos from dichloromethane solution, which suggests that both the amino group and PO part of these molecules is responsible for interaction with the imprinted polymer. Evidence was also presented by FT-IR analysis that the amide-hydrogen-bonding interaction between the MIP-coated films and monocrotophos was originated for monocrotophos recognition. To achieve selective extraction of monocrotophos from sample, stir bars coated with MIP films were washed with 10% (v/v) acetic acid/methanol and methanol. Clean extracts and yields of 95% were obtained, demonstrating the suitability of stir bar coated with MIP films for the analysis of environmental and biological samples. Compared with traditional MIP and SBSE, the MIP-coated film showed not only the high selectivity but also the rapid equilibrium adsorption.

Two-step simultaneous distillation and solvent extraction for isolation both free and bound aroma in tobacco.

In this investigation, a novel two-step simultaneous distillation and solvent extraction (two-step SDE) method was developed to isolate both free and bound aroma in tobacco. Firstly, free aroma were extracted into dichloromethane by SDE for 4 h with SDE sample solution at pH 5.5. Then the SDE sample solution was adjusted to pH 2.5, bound aroma were hydrolyzed, and released as free aroma extracted by fresh dichloromethane. Following, both the free and bound aroma were analyzed by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). The whole isolation procedure of both free and bound aroma was carried out in one SDE apparatus and using one same sample. Especially, the procedure of isolation of bound aroma was greatly simplified. To apply and validate the proposed two-step SDE method, a traditional method were also used to isolate the bound aroma. The total bound aroma obtained by the proposed two-step SDE method and the traditional method were 119.83 mg kg(-1) and 88.9 mg kg(-1), respectively. For isolation of bound aroma, the proposed two-step SDE method was of better extraction recovery, less labourious, solvent and time consuming than the traditional method.

[Spectroscopic characterization of structure of cerium incorporated MCM-48 mesoporous molecular sieve].

Cerium incorporated MCM-48 molecular sieves have been hydrothermally synthesized using a mixed template and pH adjusting route. The samples were characterized by various physicochemical methods, including X-ray diffraction, diffuse reflectance UV-Vis spectroscopy, FTIR spectroscopy, XRF spectroscopy, and nitrogen adsorption. These results reveal that cerium is incorporated in MCM-48 and it is in the form of well-dispersed tetra-coodinated cerium ion. The proper concentration of cerium and adjusting pH can keep Ce-MCM-48 with higher specific surface area , larger unit-cell parameter, narrower pore-size distribution, and thicker pore wall than those of MCM-48. These deduce higher activity, and better selectivity, thermal stability and hydrothermal stability than those of MCM-48. The concentration of Ce incorporated in MCM-48 affects the vibration of the framewoke Si of molecular sieves.

A new molecularly imprinted polymer for selective extraction of cotinine from urine samples by solid-phase extraction.

Cotinine, the main metabolite of nicotine in human body, is widely used as a biomarker for assessment of direct or passive exposure to tobacco smoke. A method for molecularly imprinted solid-phase extraction (MISPE) of cotinine from human urine has been investigated. The molecularly imprinted polymer (MIP) with good selectivity and affinity for cotinine was synthesized using cotinine as the template molecule, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross-linker. The imprinted polymer was evaluated for use as a SPE sorbent, in tests with aqueous standards, by comparing recovery data obtained using the imprinted form of the polymer and a non-imprinted form (NIP). Extraction from the aqueous solutions resulted in more than 80% recovery. A range of linearity for cotinine between 0.05 and 5 microg mL-1 was obtained by loading 1 mL blank urine samples spiked with cotinine at different concentrations in acetate buffer of pH 9.0, and by using double basic washing and acidic elution. The intra-day coefficient of variation (CV) was below 7% and inter-day CV was below 10%. This investigation has provided a reliable MISPE-HPLC method for determination of cotinine in human urine from both active smokers and passive smokers.

Photoacoustic phase study on the frequency dependence of phase angle and triplet state lifetime of Nd(III)-acetylacetonate.

The amplitude and phase of the photoacoustic (PA) signal generated in the rare earth complex powder of Nd(III)-acetylacetonate (Nd(AA)3) were examined. By using the reasonably simplified formula about phase angle at the wavelengths assigned to pi-pi* transition of ligand and f-f transitions of Nd3+, the instrumental contribution to phase angle at different chopping frequency was calculated. The frequency dependence of sample phase angle, the relative phase angle shift caused by instrumental factors and the calculation of triplet state lifetime of sample under study were also discussed. Being independent of sample, the instrumental contribution to phase angle was regarded as a parameter representing the situations of instruments and measurement and it became an approach to calculate the relaxation time of ligand in rare earth complex.

Optimization of microwave-assisted solvent extraction for volatile organic acids in tobacco and its comparison with conventional extraction methods.

In the present study, a new method using microwave-assisted solvent extraction (MASE) technique followed directly GC analysis was developed for the extraction of volatile organic acids (VOAs) in tobacco. The MASE conditions (heating time, volume of extracting solvent and extraction temperature) were optimized by means of an orthogonal array design (OAD) procedure. The results suggested that extractant, temperature and heating time were statistically the most significant factors. The extracts were directly analyzed with capillary GC operating in splitless-injection mode on an Agilent HP-FFAP capillary column. Under optimum operating conditions, MASE showed significantly better recoveries than those obtained by the conventional extraction method (ultrasonic and reflux extraction), ranging from 90.6% to 103.2%. In addition, a drastic reduction of the extraction time (20 min versus 4h) and solvent consumption (20 mL versus 100 mL) was achieved with an outstanding reproducibility (CV < or =5%).